Rate Equations for Reversible Disproportionation Reactions and Fitting to Timecourse Data

Abstract

Integrated rate equations are straightforward to fit to experimental data to verify a proposed mechanism and extract kinetic parameters. Such equations are derived for reversible disproportionation/comproportionation reactions with any set of initial concentrations. Extraction of forward and reverse rate constants from experimental data by fitting the rate law to the data are demonstrated for the disproportionation of TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) under acidic conditions where the approach to equilibrium is observed.